# US 8,772,519 B2 · Process for preparing mono-allyl-functionalized dialkylphosphinic acids, salts and esters thereof with allylic compounds, and the use thereof

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- Number: US 8,772,519 B2
- Document ID: US8772519B2
- Status: Granted
- Kind: B2
- Application number: 13/127,110
- Filed: 2009-10-06
- Published: 2011-09-01
- Granted: 2014-07-08
- Earliest claimed: 2008-11-11
- Assignees: Clariant Finance (BVI) Limited
- Applicants: Michael Hill; Werner Krause; Martin Sicken
- Inventors: Michael Hill; Werner Krause; Martin Sicken
- Web page: https://patentgrep.com/patent/US8772519B2

## CPC

- C09K 21/12: containing phosphorus
- C07F 9/302: {Acyclic unsaturated acids}
- C07F 9/3217: {Esters of acyclic unsaturated acids}
- C08K 5/5313: Phosphinic compounds, e.g. R2=P(:O)OR'
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The invention relates to a process for preparing mono-allyl-functionalized dialkylphosphinic acids, esters and salts with allylic compounds, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, or salt or ester thereof (II), b) the alkylphosphonous acid, or salt or ester thereof (II) thus formed is reacted with allylic compounds of the formula (V) in the presence of a catalyst B and of a base to give a mono-allyl-functionalized dialkylphosphinic acid derivative (III), where R1, R2, R3, R4, R5, R6, R7, R8, R9 are the same or different and are each independently, inter alia, H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, and X is H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogen base, and the catalysts A and B are transition metals and/or transition metal compounds and/or catalyst systems which are composed of a transition metal and/or a transition metal compound and at least one ligand.

## Claims

### Claim 1

A method for producing monoallyl-functionalized dialkylphosphinic acids, esters or salts with allylic compounds, comprising the steps of
a) reacting a phosphinic acid source (I)
with one or more olefins (IV)
in the presence of a catalyst A to form an alkylphosphonous acid, salt or ester (II)
b) reacting the alkylphosphonous acid, salt or ester (II) with one or more allylic compounds of the formula (V)
in the presence of a catalyst B and a base to form a monoallyl-functionalized dialkylphosphinic acid derivative (III)
where R1, R2, R3, R4, R5, R6, R7, R8, R9 are identical or different and are each independently H, C1-C18-alkyl, C6-C18-aryl, C6-C1-aralkyl, C6-C18-alkylaryl, CN, CHO, OC(O)CH2CN, CH(OH)C2H5, CH2CH(OH)CH3, 9-anthracene, 2-pyrrolidone, (CH2)mOH, (CH2)mNH2, (CH2)mNCS, (CH2)mNC(S)NH2, (CH2)mSH, (CH2)mS-2-thiazoline, (CH2)mSiMe3, C(O)R10, (CH2)mC(O)R10, CH═CHR10 or CH═CH—C(O)R10 and where R10 is C1-C8-alkyl or C6-C18-aryl and m is an integer from 0 to 10 and X is H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, (CH2)kOH, CH2—CHOH—CH2OH, (CH2)kO(CH2)kH, (CH2)k—CH(OH)—(CH2)kH, (CH2—CH2O)kH, (CH2—C[CH3]HO)kH, (CH2—C[CH3]HO)k(CH2—CH2O)kH(CH2—CH2O)k(CH2—C[CH3]HO)H, (CH2—CH2O)k-alkyl, (CH2—C[CH3]HO)k-alkyl, (CH2—C[CH3]HO)k(CH2—CH2O)k-alkyl, (CH2—CH2O)k(CH2—C[CH3]HO)O-alkyl, (CH2)k—CH═CH(CH2)kH, (CH2)kNH2, (CH2)kN[(CH2)kH]2 or a combination thereof, where k is an integer from 0 to 10, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K, H a protonated nitrogen base or a combination thereof and Y is a halogen or acetate and the catalysts A and B are transition metals, transition metal compounds, catalyst systems composed of a transition metal, transition metal compound or combination thereof and at least one ligand or a combination thereof.

### Claim 2 (depends on 1)

The method according to claim 1 wherein the monoallyl-functionalized dialkylphosphinic acid, its salt or ester (III) obtained after step b) is subsequently reacted in a step c) with metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K a protonated nitrogen base or a combination thereof to form the corresponding monoallyl-functionalized dialkylphosphinic acid salts (III) of these metals, of a nitrogen compound or a combination thereof.

### Claim 3 (depends on 1)

The method according to claim 1 wherein the alkylphosphonous acid, salt or ester (II) obtained after step a), the monoallyl-functionalized dialkylphosphinic acid, salt or ester (III) obtained after step b), the reaction solution thereof or a combination thereof are esterified with an alkylene oxide or an alcohol M-OH, M′-OH or a combination thereof, and the alkylphosphonous ester (II), monoallyl-functionalized dialkylphosphinic ester (III) or a combination thereof are subjected to the reaction steps b) or c).

### Claim 4 (depends on 1)

The method according to claim 1, wherein the groups C6-C18-aryl, C6-C18-aralkyl and C6-C18-alkylaryl are substituted with SO3X2, —C(O)CH3, OH, CH2OH, CH3SO3X2, PO3X2, NH2, NO2, OCH3, SHOC(O)CH3 or a combination thereof.

### Claim 5 (depends on 1)

The method according to claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 are identical or different and are each independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.

### Claim 6 (depends on 1)

The method according to claim 1, wherein X is H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol, propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl, glycerol or a combination thereof.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the transition metals, transition metal compounds or a combination thereof are from the seventh or eighth transition groups.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the transition metals, transition metal compounds or combination thereof are rhodium, nickel, palladium, platinum or ruthenium.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the one or more allylic compounds are 3-chloro-1-propene, 3-chloro-2-methyl-1-propene, 3-chloro-1-phenyl-1-propene, 1-chloro-2-butene, 1-chloro-3-methyl-2-butene, 3-bromo-1-propene, 3-bromo-2-methyl-1-propene, 3-bromo-1-phenyl-1-propene, 1-bromo-2-butene, 1-bromo-3-methyl-2-butene, allyl acetate, 2-methylallyl acetate or a combination thereof.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the base is selected from the group consisting of an alkali, alkaline earth metals, alkali metal hydrides, alkoxides, hydroxides, alkaline earth metal hydrides, alkoxides, hydroxides, amines, diamines and organolithium compounds.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the alcohol of the general formula M-OH is a linear or branched, saturated or an 4 unsaturated, monohydric organic alcohol having a carbon chain length of C1-C18 and the alcohol of the general formula M′-OH is a linear or branched, saturated or unsaturated polyhydric organic alcohol having a carbon chain length of C1-C18.